Structural studies of high dispersion H3PW12O40/SiO2 solid acid catalysts

Highly dispersed H3PW12O40/SiO2 catalysts with loadings between 3.6 and 62.5 wt% have been synthesised and characterised. The formation of a chemically distinct interfacial HPW species is identified by XPS, attributed to pertubation of W atoms within the Keggin cage in direct contact with the SiO2 surface. EXAFS confirms the Keggin unit remains intact for all loadings, while NH3 adsorption calorimetery reveals the acid strength >0.14 monolayers of HPW is loading invariant with initial ΔHads = −164 kJ mol−1. Lower loading catalysts exhibit weaker acidity which is attributed to an inability of highly dispersed clusters to form crystalline water. For reactions involving non-polar hydrocarbons the interfacial species where the accessible tungstate is highest confer the greatest reactivity, while polar chemistry is favoured by higher loadings which can take advantage of the H3PW12O40 pseudo-liquid phase available within supported multilayers. © the Owner Societies 2006.

On the thermal stabilization of carbon-supported SiO2 catalysts by phosphorus:evaluation in the oxidative dehydrogenation of ethylbenzene to styrene and a comparison with relevant catalysts

A strategy to enhance the thermal stability of C/SiO2 hybrids for the O2-based oxidative dehydrogenation of ethylbenzene to styrene (ST) by P addition is proposed. The preparation consists of the polymerization of furfuryl alcohol (FA) on a mesoporous precipitated SiO2. The polymerization is catalyzed by oxalic acid (OA) at 160 °C (FA:OA = 250). Phosphorous was added as H3PO4 after the polymerization and before the pyrolysis that was carried out at 700 °C and will extend the overall activation procedure. Estimation of the apparent activation energies reveals that P enhances the thermal stability under air oxidation, which is a good indication for the ODH tests. Catalytic tests show that the P/C/SiO2 hybrids are readily active, selective and indeed stable in the applied reactions conditions for 60 h time on stream. Coke build-up during the reaction attributed to the P-based acidity is substantial, leading to a reduction of the surface area and pore volume. The comparison with a conventional MWCNT evidences that the P/C/SiO2 hybrids are more active and selective at high temperatures (450–475 °C) while the difference becomes negligible at lower temperature. However, the comparison with reference P/SiO2 counterparts shows a very similar yield than the hybrids but more selective to ST. The benefit of the P/C/SiO2 hybrid is the lack of stabilization period, which is observed for the P/SiO2 to create an active coke overlayer. For long term operation, P/SiO2 appears to be a better choice in terms of selectivity, which is crucial for commercialization.

Non-invasive phakometric measurement of corneal and crystalline lens alignment in human eyes

We describe a non-invasive phakometric method for determining corneal axis rotation relative to the visual axis (β) together with crystalline lens axis tilt (α) and decentration (d) relative to the corneal axis. This does not require corneal contact A-scan ultrasonography for the measurement of intraocular surface separations. Theoretical inherent errors of the method, evaluated by ray tracing through schematic eyes incorporating the full range of human ocular component variations, were found to be larger than the measurement errors (β < 0.67°, α < 0.72° and d < 0.08 mm) observed in nine human eyes with known ocular component dimensions. Intersubject variations (mean ± S.D.: β = 6.2 ± 3.4° temporal, α = 0.2 ± 1.8° temporal and d = 0.1 ± 0.1 mm temporal) and repeatability (1.96 × S.D. of difference between repeat readings: β ± 2.0°, α ± 1.8° and d ± 0.2 mm) were studied by measuring the left eyes of 45 subjects (aged 18-42 years, 29 females and 16 males, 15 Caucasians, 29 Indian Asians, one African, refractive error range -7.25 to +1.25 D mean spherical equivalent) on two occasions. © 2005 The College of Optometrists.

Three-dimensional magnetic resonance imaging of the phakic crystalline lens during accommodation

To quantify changes in crystalline lens curvature, thickness, equatorial diameter, surface area, and volume during accommodation using a novel two-dimensional magnetic resonance imaging (MRI) paradigm to generate a complete three-dimensional crystalline lens surface model.

A sensitivity study of the human crystalline lens using finite element analysis

Finite element analysis is a useful tool in understanding how the accommodation system of the eye works. Further to simpler FEA models that have been used hitherto, this paper describes a sensitivity study which aims to understand which parameters of the crystalline lens are key to developing an accurate model of the accommodation system. A number of lens models were created, allowing the mechanical properties, internal structure and outer geometry to be varied. These models were then spun about their axes, and the deformations determined. The results showed the mechanical properties are the critical parameters, with the internal structure secondary. Further research is needed to fully understand how the internal structure and properties interact to affect lens deformation.

On the active site in H3PW12O40/SiO2 catalysts for fine chemical synthesis

The surface environment and structural evolution of silica supported phosphotungstic acid (H3PW12O40) catalysts have been investigated as a function of acid loading. H3PW12O40 clusters are deposited intact upon the silica surface, adopting a Stranksi-Krastanov growth mode forming a two-dimensional adlayer which saturates at 45wt% acid. Intimate contact with the silica support perturbs the local chemical environment of three tungstate centres, which become inequivalent with those in the remaining cluster, suggesting an adsorption mode involving three terminal W==O groups. Above the monolayer, H3PW12O40 clusters form three-dimensional crystallites with physico-chemical properties indistinguishable from those in the bulk heteropoly acid. These H3PW12O40/SiO2 materials are efficient for the solventless isomerisation of α-pinene under mild reaction conditions. Activity scales directly with the number of accessible perturbed tungstate sites at the silica interface; these are the active species.

Experimental and theoretical studies on six-membered ring hydrogen bond systems in crystalline drug substances

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Experimental and theoretical studies on molecular geometry and polymorphism in crystalline drug substances

DUE TO COPYRIGHT RESTRICTIONS ONLY AVAILABLE FOR CONSULTATION AT ASTON UNIVERSITY LIBRARY AND INFORMATION SERVICES WITH PRIOR ARRANGEMENT

Analysis of femtosecond laser surface patterning on bulk single-crystalline diamond

Preliminary work is reported on 2-D and 3-D microstructures written directly with a Yb:YAG 1026 nm femtosecond (fs) laser on bulk chemical vapour deposition (CVD) single-crystalline diamond. Smooth graphitic lines and other structures were written on the surface of a CVD diamond sample with a thickness of 0.7mm under low laser fluences. This capability opens up the opportunity for making electronic devices and micro-electromechanical structures on diamond substrates. The fabrication process was optimised through testing a range of laser energies at a 100 kHz repetition rate with sub-500fs pulses. These graphitic lines and structures have been characterised using optical microscopy, Raman spectroscopy, X-ray photoelectron spectroscopy and atomic force microscopy. Using these analysis techniques, the formation of sp2 and sp3 bonds is explored and the ratio between sp2 and sp3 bonds after fs laser patterning is quantified. We present the early findings from this study and characterise the relationship between the graphitic line formation and the different fs laser exposure conditions. © 2012 Taylor & Francis.

A holistic multi evidence approach to study the fragmentation behaviour of crystalline mannitol

Mannitol is an essential excipient employed in orally disintegrating tablets due to its high palatability. However its fundamental disadvantage is its fragmentation during direct compression, producing mechanically weak tablets. The primary aim of this study was to assess the fracture behaviour of crystalline mannitol in relation to the energy input during direct compression, utilising ball milling as the method of energy input, whilst assessing tablet characteristics of post-milled powders. Results indicated that crystalline mannitol fractured at the hydrophilic (011) plane, as observed through SEM, alongside a reduction in dispersive surface energy. Disintegration times of post-milled tablets were reduced due to the exposure of the hydrophilic plane, whilst more robust tablets were produced. This was shown through higher tablet hardness and increased plastic deformation profiles of the post-milled powders, as observed with a lower yield pressure through an out-of-die Heckel analysis. Evaluation of crystal state using x-ray diffraction/differential scanning calorimetry showed that mannitol predominantly retained the β-polymorph; however x-ray diffraction provided a novel method to calculate energy input into the powders during ball milling. It can be concluded that particle size reduction is a pragmatic strategy to overcome the current limitation of mannitol fragmentation and provide improvements in tablet properties.

Probing crystallisation of a fluoro-apatite - mullite system using neutron diffraction

Real-time small angle neutron scattering and wide angle neutron scattering studies were undertaken concurrently on a glass ionomer of nominal composition 4.5(SiO2)-3(Al2O3)-1.5(P2O5)-3(CaO)-2(CaF2). Neutron studies were conducted as a function of temperature to investigate the crystallisation process. No amorphous phase separation was observed at room temperature and the onset of crystallisation was found to occur at 650°C, which is 90°C lower than previously reported. The first crystalline phase observed corresponded to fluorapatite; it was only upon further heating was the mullite phase became present. The crystallite size at 650°C was found to be ~115Å and the result was consistent across all measurements.

Application of staged O2 feeding in the oxidative dehydrogenation of ethylbenzene to styrene over Al2O3 and P2O5/SiO2 catalysts

Drastic improvements in styrene yield and selectivity were achieved in the oxidative dehydrogenation of ethylbenzene by staged feeding of O2. Six isothermal packed bed reactors were used in series with intermediate feeding of O2, while all EB was fed to the first reactor, diluted with helium or CO2 (1:5 molar ratio), resulting in total O2:EB molar feed ratios of 0.2-0.6. The two catalyst samples, γ-Al 2O3 and 5P/SiO2, that were applied both benefitted from this operation mode. The ethylbenzene conversion per stage and the selectivity to styrene were significantly improved. The production of COX was effectively reduced, while the selectivity to other side products remained unchanged. Compared with co-feeding at a total O 2:EB molar feed ratio of 0.6, by staged feeding the EB conversion (+15% points for both catalysts), ST selectivity (+4% points for both samples) and O2 (ST) selectivity (+9% points for γ-Al2O 3 and +17% points for 5P/SiO2) all improved. The ethylbenzene conversion over 5P/SiO2 can be increased from 18% to 70% by increasing the number of reactors from 1 to 6 with each reactor a total amount of O2 of 0.1 without the loss of ST selectivity (93%). For 5P/SiO2 a higher temperature (500 C vs. 450 C for Al 2O3) is required. Essentially more catalyst (5P/SiO 2) was required to achieve full O2 conversion in each reactor. Staged feeding of O2 does not eliminate the existing issues of the catalyst stability both in time-on stream and as a function of the number of catalyst regenerations (5P/SiO2), or the relatively moderate performance (relatively low styrene selectivity for γ-Al2O 3). © 2014 Elsevier B.V.

Acetic acid ketonization over Fe3O4/SiO2 for pyrolysis bio-oil upgrading

A family of silica supported, magnetite nanoparticle catalysts was synthesized and investigated for continuous flow acetic acid ketonization as a model pyrolysis bio-oil upgrading reaction. Physicochemical properties of Fe3O4/SiO2 catalysts were characterized by HRTEM, XAS, XPS, DRIFTS, TGA and porosimetry. Acid site densities were inversely proportional to Fe3O4 particle size, although acid strength and Lewis character were size invariant, and correlated with the specific activity for vapor phase acetic ketonization to acetone. A constant activation energy (~110 kJ.mol-1), turnover frequency (~13 h-1) and selectivity to acetone of 60 % were observed for ketonization across the catalyst series, implicating Fe3O4 as the principal active component of Red Mud waste.